WO2018058505A1 - Compositions pouvant durcir par rayonnement ayant des propriétés anti-taches - Google Patents

Compositions pouvant durcir par rayonnement ayant des propriétés anti-taches Download PDF

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Publication number
WO2018058505A1
WO2018058505A1 PCT/CN2016/101034 CN2016101034W WO2018058505A1 WO 2018058505 A1 WO2018058505 A1 WO 2018058505A1 CN 2016101034 W CN2016101034 W CN 2016101034W WO 2018058505 A1 WO2018058505 A1 WO 2018058505A1
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meth
compounds
radiation curable
curable composition
weight
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PCT/CN2016/101034
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English (en)
Inventor
Xie Cheng
Steven Cappelle
Peter BURIE
Dong Chen
Rong Chen
Original Assignee
Allnex Belgium S.A.
Allnex Resins (Shanghai) Co., Ltd.
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Application filed by Allnex Belgium S.A., Allnex Resins (Shanghai) Co., Ltd. filed Critical Allnex Belgium S.A.
Priority to PCT/CN2016/101034 priority Critical patent/WO2018058505A1/fr
Priority to EP17855011.7A priority patent/EP3519493B1/fr
Priority to CN201780060526.0A priority patent/CN109844004B/zh
Priority to US16/334,424 priority patent/US11359110B2/en
Priority to PCT/CN2017/104568 priority patent/WO2018059561A1/fr
Priority to TW106133549A priority patent/TWI791464B/zh
Publication of WO2018058505A1 publication Critical patent/WO2018058505A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/61—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C08G18/6725—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing ester groups other than acrylate or alkylacrylate ester groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/54—Inks based on two liquids, one liquid being the ink, the other liquid being a reaction solution, a fixer or a treatment solution for the ink
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/106—Esters of polycondensation macromers
    • C08F222/1065—Esters of polycondensation macromers of alcohol terminated (poly)urethanes, e.g. urethane(meth)acrylates

Definitions

  • the present invention relates to radiation curable compositions (I) for producing coatings, inks and overprint varnishes with excellent anti-stain properties, to their use and preparation.
  • the compositions (I) of the invention are compatible with standard radiation curable materials. They allow to obtain excellent anti-stain properties for high gloss coatings as well as for matte coatings (II) with a gloss level at 60° of at most 15, even at most 10.
  • Plastics coatings represent a significant and high growth segment of the coating industry and target the challenging requests for advanced surface finish technologies covering aesthetics as well as additional protective & functional features.
  • the radiation curing technology has been used successfully in this industry for over 30 years and is especially renowned for superior hardcoat properties.
  • a silicone or fluoro additive with low surface energy is added into hardcoat formulations to obtain anti-stain and/or anti-graffiti properties.
  • said additives have bad miscibility/compatibility with the hardcoating matrix.
  • it it’s challenging to balance the scratch/abrasion resistance and anti-stain or anti-graffiti properties, especially for low gloss coating with a gloss level at 60° of at most 15 or lower.
  • WO14/186135 discloses adhesive films for producing graphics comprising a polymeric film layer having on one major side a colored adhesive layer and on the opposite major side an anti-graffiti coating;
  • the anti-graffiti coating is based on the (a) a major amount (>50 wt%) of one or more compounds having at least two free radical polymerizable groups and (b) a minor amount of one or more polysiloxane additives having two or more free radical polymerizable groups.
  • No hardcoats are disclosed in this patent application. Coatings described have a high gloss finish.
  • EP2583986 describes fluorinated compounds showing very good miscibility/compatibility with an active energy curable matrix and excellent anti-stain or anti-graffiti properties in high gloss coatings. However, when these materials are used in coatings with a gloss level at 60° of at most 15 or lower, then the anti-stain or anti-graffiti properties are not good enough. Furthermore, the formed thin stain resistance layers are easily damaged due to abrasion or scratch.
  • composition (I) optionally, from 0 to 60%by weight of at least one compound (C) different from (A) and (B) , wherein the weight percentages are on the total weight of the composition (I) .
  • the amount of compounds (A) in the composition (I) is from 15 to 75%by weight (wt%) .
  • the amount of compounds (B) used therein is from 0.8 to 50 w%.
  • compounds (C) typically are used in an amount from 10 to 60 wt%, more particular from 15 to 55 wt%.
  • the radiation curable composition (I) consists essentially of:
  • composition (I) optionally, from 0 to 60 wt%of at least one compound (C) different from (A) and (B) , wherein the weight percentages are on the total weight of the composition (I) .
  • composition (I) of the invention is comprised for at least 90 %by weight (wt%) , preferably by at least 95 wt%, more preferably by at least 98 wt%, even more preferably by at least 99 wt%of compounds (A) , (B) , and where present (C) . Most typically the weight percentages of (A) , (B) , and where present (C) sum up to 100%.
  • (meth) acrylated compound is meant a compound that comprises at least one (meth) acryloyl group.
  • (meth) acryloyl is meant acryloyl, methacryloyl or a mixture of both.
  • the at least one silicone-modified urethane (meth) acrylate (A) typically is prepared from:
  • the silicone-modified urethane (meth) acrylate (A) is further prepared from a further compound (iv) with at least one isocyanate reactive group, that is different from any of compounds (i) to (iii) .
  • the isocyanate reactive groups typically are: hydroxyl groups, amino groups and /or thiol groups (see below) .
  • compounds (iv) comprise at least two hydroxyl groups per molecule and are for instance selected from one or more of: hydroxyl group containing polyester (meth) acrylates, hydroxyl group containing polyether (meth) acrylates, hydroxyl group containing polyether ester (meth) acrylates, hydroxyl group containing polyepoxy (meth) acrylates and hydroxyl group containing (meth) acrylated (meth) acrylics.
  • such compounds have a hydroxyl functionality of 2 or higher.
  • compounds (iv) are being used to prepare urethane (meth) acrylates (A) according to the invention.
  • no compounds (iv) are being used to prepare urethane (meth) acrylates (A) according to the invention.
  • Polysiloxanes (i) according to the invention have at least one isocyanate reactive group, typically at least 2 isocyanate reactive groups. Often they comprise two isocyanate reactive groups per molecule.
  • isocyanate reactive group' or the term ‘reactive group capable to react with isocyanate groups’ is meant a functional group that will react with an isocyanate group under typical reactive conditions for reacting an isocyanate group. Examples of such groups are: hydroxyl groups, amino groups and/or thiol groups. Preferred in the context of the invention are amino groups and/or hydroxyl groups. Amino groups can be –NH or –NH2 groups. Most preferred however are hydroxyl groups. Most typically polysiloxanes (i) of the invention are diols
  • Suitable polysiloxanes (i) include: linear or branched polydialkyl siloxanes, linear or branched polyalkylaryl siloxanes and/or linear or branched polydiarylsiloxanes. Preferred are polydialkyl siloxanes which may be linear or branched but most typically are linear.
  • the isocyanate reactive groups can be situated at the end of the polymer chain, i.e. in the end group of the polymer backbone and/or in a terminal portion of side chains.
  • the isocyanate reactive groups (typically hydroxyl groups) are comprised in the end groups of the polysiloxane backbone.
  • polysiloxanes (i) that comprise one or more hydroxyl groups.
  • hydroxyl terminated polydialkyl siloxanes and even more in particular linear hydroxyl terminated polydialkyl siloxanes.
  • hydroxyl groups are present at both terminal ends.
  • the ‘alkyl’ group most typically is a C1 to C4 alkyl group and most typically is a methyl group.
  • compounds (i) of the invention can comprise one or more fluoro groups.
  • Polysiloxanes (i) according to the invention can hence be fluoro-modified polysiloxanes or fluorinated polysiloxanes. In another embodiment, however, the polysiloxanes (i) do not comprise any fluoro groups.
  • Polysiloxanes (i) according to the invention may bear a certain amount of alkoxy groups such as ethoxy (EO) and/or propoxy (PO) groups.
  • alkoxy groups such as ethoxy (EO) and/or propoxy (PO) groups.
  • Preferred in the context of the invention are polysiloxanes (i) according to Formula I:
  • ‘a’ is an integer from 1 to 250, preferably from 1 to 150, more preferably from 1 to 100; wherein ‘b’ is an integer from 0 to 100, preferably from 0 to 50, more preferably from 0 to 30 and most preferably from 0 to at most 20; wherein ‘c’ and ‘d’ are integers from 0 to 200, preferably from 0 to 150, more preferably from 0 to 100 and most preferably from 0 to at most 50; and wherein ‘e’ is an integer from 0 to 50, preferably from 0 to 50, more preferably from 0 to 35 and most preferably from 0 to at most 20.
  • ‘a’ is an integer from 1 to 250, preferably from 1 to 150, more preferably from 1 to 100; and wherein ‘c’ and ‘d’ are integers from 0 to 200, preferably from 0 to 150, more preferably from 0 to 100 and most preferably from 0 to at most 50.
  • the polysiloxanes (i) of the invention having at least one isocyanate reactive group comprise between 5 and 100 -SiO-units, more preferably between 5 and 70 -SiO-units.
  • polysiloxanes (i) include but are not limited to IM11, IM15, IM22, IM47 (diols) , FLUID NH 15 D, FLUID NH 40D, FLUID NH 130D (diamines) , FLUID OH 15D, FLUID OH 40D (hydroxyl) (all available from Wacker, Germany) , KF-8010, X-22-161A, X-22-161B, KF-8012, KF-8008 (diamine end groups) , KF-665, KF-664 (amine-ending pendent groups) , X-22-167B (dithiol end groups) , KF-2001, KF-2004 (thiol-ending pendent groups) KF-6001 and KF-6002 (diols) (all available from Shin-Etsu, Japan) , Silmer OH10, Fluorosil C7-F, Silsurf Di-2510, Sil
  • Polysiloxanes (i) of the invention typically have a molecular weight MW of between 700 and 40.000 Daltons. Usually the MW is at most 20.000 Daltons, typically at most 12.000 Daltons, and most typically at most 9.000 Daltons. Molecular weights MW can be measured by gel permeation chromatography using polystyrene standards but most typically they are calculated from the target molecule.
  • hydroxyl value (IOH) of polysiloxanes (i) of the invention is between 1 and 500, more preferably between 5 and 250, even more preferably of between 5 and 150.
  • polyisocyanate is meant to designate a compound containing at least two isocyanate groups.
  • the polyisocyanate contains not more than six isocyanate groups, more preferably however not more than three isocyanate groups.
  • Aromatic, araliphatic, aliphatic or cycloaliphatic polyisocyanates and mixtures of such isocyanates may be used.
  • Suitable isocyanates include xylylene diisocyanate, tetramethylene diisocyanate, 1, 4-diisocyantobutane, 1, 12-diisocyanatododecane, pentamethylene diisocyanate, hexamethylene diisocyanate, 2, 3, 3-trimethylhexamethylene diisocyanate, 2, 2, 4-and 2, 4, 4-trimethyl-hexamethylene diisocyanate, 1, 4-cyclohexylene diisocyanate, 4, 4'-dicyclohexylmethane diisocyanate, 4, 4'-dicyclohexyl diisocyanate, 1-diisocyanato-3, 3, 5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate) , 1, 4-phenylene diisocyanate, 2, 6-tolylene diisocyanate, 2, 4-tolylene diisocyanate, 1, 5-naphthylene diisocyanate,
  • monomeric tri-isocyanates such as 4-isocyanatomethyl-1, 8-octamethylene diisocyanate or triphenylmethane 4, 4', 4"-triisocyanate.
  • Polyisocyanate adducts containing isocyanurate, iminooxadiazine dione, urethane, biuret, allophanate, uretidione and/or carbodiimide groups are also useful as the isocyanate component (ii) .
  • Such polyisocyanates may have isocyanate functionalities of 3 or more.
  • Such isocyanates are prepared by the trimerization or oligomerization of di-isocyanates or by the reaction of di-isocyanates with polyfunctional compounds containing hydroxyl or amine groups.
  • aliphatic and/or cycloaliphatic polyisocyanates Preferred in the context of the invention are aliphatic and/or cycloaliphatic polyisocyanates. Most preferred are aliphatic polyisocyanates (ii) . Di-isocyanates and more in particular aliphatic di-isocyanates are generally preferred such as isophorone di-isocyanate. In addition to di-isocyanates, tri-and higher functional isocyanates can be used. Useful examples include isocyanurates e.g., cyclic trimer of hexamethylene di-isocyanate and cyclic trimer of isophorone di-isocyanate, and biurets containing tri-isocyanates.
  • Compounds (iii) according to the invention are in general hydroxyl functional (meth) acrylates and more in particular ‘ (meth) acryloyl mono-hydroxy’ compounds, whereby is meant to designate compounds comprising one hydroxyl group and one or more (meth) acryloyl groups. Often these compounds comprise two or more (meth) acryloyl groups, even three or more (meth) acryloyl groups. Acrylates are particularly preferred. Typically compounds (iii) are different from compounds (i) and where present compounds (iv) .
  • Suitable are for instance the esterification products of aliphatic and/or aromatic polyols with (meth) acrylic acid having a residual average hydroxyl functionality of about 1.
  • Suitable hydroxyl functional (meth) acrylates (iii) include but are not limited to hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, polyethyleneoxide mono (meth) acrylate, polypropyleneoxide mono (meth) acrylate, or any of those hydroxylated monomers further reacted with lactones or lactides which add to these hydroxyls in a ring-opening reaction.
  • Suitable are also the esterification products of aliphatic and/or aromatic polyols with (meth) acrylic acid having a residual average hydroxyl functionality of about 1 or higher.
  • the partial esterification products of (meth) acrylic acid with tri-, tetra-, penta-or hexahydric polyols or mixtures thereof are preferred but it is also possible to use reaction products of such polyols with ethylene oxide and/or propylene oxide or mixtures thereof, or the reaction products of such polyols with lactones or lactides which add to these polyols in a ring-opening reaction until the desired residual hydroxyl functionality is reached.
  • Suitable compounds (ii) are for instance the (meth) acrylic esters of linear and branched polyols in which at least one hydroxy functionality remains free.
  • Preferred in the context of the invention are mono hydroxy poly (meth) acryoly compounds, whereby is meant to designate compounds comprising on average one hydroxyl groups and at least two (meth) acryloyl groups.
  • PTIA pentaerythritol triacrylate
  • PTIA pentaerythritol triacrylate
  • PTIA poly) ethoxylated and/or (poly) propoxylated pentaerythritol triacrylate and mixtures of both.
  • one or more compounds (iii) (a) are used in combination with one or more compounds (iii) (b) that bear one (or on average one) hydroxyl group and 2 (meth) acryloyl groups per molecule such as glycerol diacrylate, trimethylolpropane diacrylate, etc.
  • the amount of polysiloxanes (i) used for the synthesis of silicone-modified urethane (meth) acrylates (A) of the invention is generally in the range of from 10 to 95 percent by weight (wt%) , preferably from 20 to 95 wt%and more preferably from 30 to 95 wt%. Weight percentages are herein relative to the total weight of compounds used to prepare the silicone-modified urethane (meth) acrylate (A) .
  • the amount of polyisocyanates (ii) used for the synthesis of silicone-modified urethane (meth) acrylates (A) of the invention is generally in the range of from 1 to 28 percent by weight (wt%) , preferably from 2 to 25 wt%and more preferably from 2 to 21 wt%. Weight percentages are herein relative to the total weight of compounds used to prepare the silicone-modified urethane (meth) acrylate (A) .
  • the amount of compounds (iii) used for the synthesis of silicone-modified urethane (meth) acrylates (A) of the invention is generally in the range of from 1 to 60 percent by weight (wt%) , preferably from 4 to 53 wt%and more preferably from 4 to 46 wt%. Weight percentages are herein relative to the total weight of compounds used to prepare the silicone-modified urethane (meth) acrylate (A) .
  • the amount of compounds (iv) used for the synthesis of the silicone-modified urethane (meth) acrylates (A) of the invention is generally in the range of from 0 to 50 percent by weight (wt%) , preferably from 0 to 40 wt%and more preferably from 0 to 30 wt%. Weight percentages are herein relative to the total weight of compounds used to prepare the silicone-modified urethane (meth) acrylate (A) .
  • the sum of the weight percentages of compounds (i) , (ii) , (iii) and (iv) equals 100%. In a preferred embodiment of the invention, however, the sum of the weight percentages of compounds (i) , (ii) , and (iii) equals 100%.
  • Compounds (A) of the invention typically have a weight average molecular weight Mw of from 1000 to 80000, more preferably from 1000 to 60000 and most preferably 1000 to 50000 Daltons. Typically the number average molecular weight is from 1000 to 40000, more preferably from 1000 to 30000 and most preferably 1000 to 25000 Daltons. Molecular weights typically are measured by gel permeation chromatography (GPC) in case of higher molecular weight molecules. Therefore, a small portion of the oligomer is dissolved in tetrahydrofuran (THF) and injected in the liquid chromatograph after a preliminary filtration.
  • GPC gel permeation chromatography
  • the components of the sample are typically eluted by the mobile phase solvent (THF) at a flow rate of 1 ml/min and separated by a combination of polystyrene-divinylbenzene columns at a temperature of 40°C.
  • THF mobile phase solvent
  • Standards of polystyrene with known molecular weight and narrow polydispersity are used to generate a calibration curve.
  • Compounds (B) of the invention comprise at least 5, typically at least 6 or more (meth) acrylolyl functional groups per molecule. Typically their functionality is at most 15, more typically at least 10.
  • compounds (B) according to the invention are characterized by an amount of (meth) acryloyl groups of at least 4 meq/g, typically at least 5 meq/g, preferably at least 6 meq/g, more preferably at least 7 meq/g, even more preferably at least 8 meq/g, and most preferably at least 9 meq/g.
  • the amount of (meth) acryloyl does not exceed 13 meg/g, more preferable does not exceed 12 meq/g.
  • Preferred in the context of the invention are (meth) acrylated compounds (B) that combine a functionality as indicated above with a degree of unsaturation as indicated above.
  • the amount of ethylenically unsaturated groups ( (meth) acryloyl groups in casu) is usually measured by nuclear magnetic resonance spectroscopy (NMR) and is expressed in meq per g of solid material.
  • NMR nuclear magnetic resonance spectroscopy
  • a sample of dry product is dissolved in N-methylpyrolidinone. This sample is submitted to 1H-NMR analysis in order to measure the molar concentration of ethylenically unsaturated groups using 1,3, 5-bromobenzene as internal standard.
  • the comparison between the peak assigned to aromatic protons of the internal standard and the peaks assigned to the ethylenically unsaturated double bonds allow to calculate the molar concentration of ethylenically unsaturated groups according to the formula (Ax B) /C wherein A is the integration of 1H double bonds provided by the sample, B is the number of moles of the internal standard in the sample and C is the integration of 1H provided by the internal standard.
  • the amount of ethylenically unsaturated groups can also be measured by a titration method following the addition of an excess of pyridinium sulfate dibromide on said unsaturated groups (within glacial acetic acid as solvent and mercury acetate as catalyst) . Said excess liberates iodine in the presence of potassium iodide and the iodine is then titrated with sodium thiosulfate.
  • compounds (B) are selected from urethane (meth) acrylates (B1) and/or polyester (meth) acrylates (B2) and/or (meth) acrylated pol (meth) yacrylics (B3) .
  • Preferred are urethane (meth) acrylates and more in particular urethane acrylates.
  • Urethane (meth) acrylates (B1) according to the invention in general are obtained from the reaction of at least one polyisocyanate (ii) , at least one (meth) acrylated (iii) containing at least one reactive group capable to react with isocyanate groups, and, optionally at least one diol (iv) as described above.
  • the reactive group capable to react with isocyanate groups is a hydroxyl group.
  • Urethane (meth) acrylates (B1) in the context of the invention are different from compounds (A) . Typically they do not contain any compounds (i) in their backbone. Typically compounds (B1) according to the invention do not comprise any silicone units or any fluoro containing groups. Typically the sum of the weight percentages of compounds (ii) and (iii) used to prepare the urethane (meth) acrylate (B1) equals 100%. In an embodiment of the invention, compounds (ii) and (iii) used for preparing compounds (B1) or the same as used in the preparation of compounds (A) .
  • urethane (meth) acrylates (B1) that are used in the invention have a molecular weight MW of between 400 and 20,000 Daltons. Usually the MW is at most 5,000 Daltons, typically at most 2,000 Daltons, and most typically at most 1,000 Daltons. Molecular weights MW can be measured by gel permeation chromatography using polystyrene standards but most typically they are calculated from the target molecule.
  • urethane (meth) acrylates are those commercialized as 1290, EB1290N, 220, 270, 264, 294/25HD, 4883, 5129, 8210, 8602, 8415, 225 and 9260. These urethane (meth) acrylates can be diluted in a reactive diluent or be used in combination with other (meth) acrylated compounds. Preferred are 1290, EB1290N, 5129, 8602, 8415, 225 and 9260.
  • Polyester (meth) acrylates (B2) used in the invention typically are obtained from the reaction of at least one polyol and at least one ethylenically unsaturated carboxylic acid (v) or a suitable equivalent.
  • suitable compounds (v) include (meth) acrylic acid, ⁇ -carboxyethyl (meth) acrylate, crotonic acid, iso-crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, 3-(meth) acrylamido-3-methylbutanoic acid, 10- (meth) acrylamido-undecanoic acid, 2-(meth) acrylamido-2-hydroxyacetic acid, vinyl acetic acid and/or allyl acetic acid.
  • Acrylic acid and methacrylic acid, used alone or in combination, are preferred.
  • polyester (meth) acrylates (B2) have a molecular weight MW of between 200 and 20,000 Daltons. Usually the MW is at most 5,000 Daltons, typically at most 1,000 Daltons, most typically at most 500 Daltons.
  • Suitable polyester (meth) acrylates (B2) are for instance those commercialized as CN2295, CN291, CN 293, CN9210, CN921, CN9400 (all available from Sartomer, France) , 450, 837, 870 820, 873 and 895 (all available from Allnex, Belgium) , Dipentaerythritol penta-/hexa-acrylate and the like.
  • (Meth) acrylated poly (meth) acrylics (B3) used in the invention typically are obtained by free-radical polymerization.
  • compounds (B3) are prepared by the radical polymerization of (meth) acrylic monomers in the presence of thermal radical initiators, transfer agents and optional (reactive) solvents; a chemical functionality is introduced on the acrylic backbone to ensure the subsequent grafting with suitable mono-or poly- (meth) acrylated compounds.
  • the (meth) acrylic oligomer bears carboxylic acid functionality and is grafted with glycidyl (meth) acrylate (or vice versa) .
  • suitable compounds (B3) include 1200, 1700 and 1701.
  • compositions (I) of the invention can further comprise at least one compound (C) that is different from compounds (A) and different from compounds (B) .
  • compounds (C) are organic solvents (C1) .
  • non-reactive organic solvents (C1) that may be used in the invention, including propylene glycol monomethylether acetate, propyleneglycol monomethylether, ethylene glycol monomethylether, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone and isopropyl alcohol.
  • Compounds (C) can also be reactive diluents (C2) , which typically are (meth) acrylated monomers.
  • Suitable examples include but are not limited to: allyl (meth) acrylate, benzyl (meth) acrylate butoxyethyl (meth) acrylate, butanediol (meth) acrylate, butoxytriethylene glycol mono (meth) acrylate, t-butylaminoethyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-cyanoethyl (meth) acrylate, cyclohexyl (meth) acrylate, 2, 3-dibromopropyl (meth) acrylate, dicyclopentenyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth
  • Preferred however are monomers with at least 2, more preferably at least 3 polymerizable functional groups such as (meth) acryloyl groups.
  • Examples of poly-unsaturated compounds from this category are trimethylolpropane tri- (meth) acrylate, glycerol tri- (meth) acrylate, pentaerythritol tri, tetra- (meth) acrylate, pentaerythritol tetra- (meth) acrylate, di-trimethylolpropane tetra- (meth) acrylate, di-pentaerythritol hexa- (meth) acrylate and their (poly) ethoxylated and/or (poly) propoxylated equivalents, as well as mixtures thereof.
  • the acrylated forms hereof are preferred. Most preferred are di-and/or tri-acrylates.
  • the amount of silicone-modified urethane (meth) acrylates (A) in compositions (I) of the invention is from 10 to 80%by weight (wt%) , more preferably from 15 to 75 wt%, and most preferably from 20 to 70 wt%.
  • the amount of (meth) acrylated compounds (B) having at least 5 (meth) acryloyl groups per molecule is from 0.5 to 60% by weight (wt%) , more preferably from 0.8 to 50 wt%, and most preferably from 1.0 to 45 wt%.
  • the amount of (meth) acrylated compounds (C) other than (A) or (B) in compositions (I) of the invention is from 0 to 60%by weight (wt%) , often from 10 to 60 w%, more preferably from 15 to 55 wt%, and most preferably from 15 to 50 wt%.
  • compositions (I) of the invention can be prepared in many different ways. For instance all compounds may be added in one pot in sequence or at the same time but there are other ways to prepare these compositions. Amounts can be added in one or more steps.
  • compounds (B) and compounds (C) where present, are added to compounds (A) .
  • part or all of compounds (B) are formed in situ during the formation of compounds (A) . In said case the compounds (ii) and (iii) from which compounds (B) are prepared are the same as the ones used in the preparation of compounds (A) .
  • Compounds (A) according to the invention may be prepared by putting the ingredients (i) , (ii) , (iii) and where present (iv) together in a 1-pot reaction. Typically however only compounds (i) , (ii) and (iii) are used to make compounds (A) . In an embodiment of the invention compounds (i) are first reacted with compounds (ii) and then with compounds (iii) . Typically compounds (A) are then prepared by reacting, in a first step, compounds (i) with an excess of compounds (ii) and by reacting, in a further step, the reaction product of step 1 with compounds (iii) .
  • Compounds (B) and (C) can then be added during or after the formation of compounds (A) .
  • the molar equivalent ratio of the isocyanate groups in compounds (ii) to the hydroxyl groups of compounds (i) used to prepare compounds (A) is from 2: 1 to 10: 1.
  • this ratio is from 2.5: 1 to 6: 1 and most typically from 2.5: 1 to 4: 1.
  • the molar equivalent ratio of isocyanate reactive groups of compounds (iii) to the remaining isocyanate groups after reaction of compounds (i) and (ii) is from 2 to 0.8. More typically however this ratio is from 1.5 to 0.9 and most typically from 1.2 to 0.9.
  • compounds (A) are prepared by reacting, in a first step, compounds (ii) with an excess of compounds (iii) and by reacting, in a further step, the reaction product of step 1 with compounds (i) .
  • Part or all of the amount of compounds (B) can then be formed in situ depending on the amount (excess) of compounds (iii) used.
  • Extra (B) and/or (C) if desired, can then be added during or after the formation of compounds (A) .
  • the molar equivalent ratio of the isocyanate groups in compounds (ii) to the hydroxyl groups of compounds (iii) used to prepare compounds (A) is from 2: 1 to 1.1: 1.
  • this ratio is from 1.8: 1 to 1.2: 1 and most typically from 1.6: 1 to 1.3: 1.
  • the molar equivalent ratio of isocyanate reactive groups of compounds (i) to the remaining isocyanate groups after reaction of compounds (i) and (ii) is from 1.2 to 0.8. More typically however this ratio is from 1.1 to 0.9 and most typically from 1.05 to 0.95.
  • the reactions can be carried out in a solvent and under conditions known in the art, typically in the presence of a catalyst.
  • Suitable catalysts include tin salts or complexes such as dibutyltin dilaurate, stannous octanoate, stannous oleate, tin dibutyldi- (2-ethyl hexanoate) , stannous chloride, salts or complexes of bismuth, zinc, zirconium, aluminum and others known in the art.
  • the amount of catalyst present will depend on the particular reaction. Generally, suitable catalyst concentrations are from about 0.001 to about 10 %by weight, particularly suitable between about 0.01 %and about 1%by weight based on the total weight of reactants.
  • compositions (I) of the invention are suitable for the preparation of a coating composition, an ink, an overprint varnish. They can also be used in the making of composite materials. An aspect of the invention relates to such use. Another aspect of the invention relates to a coating composition, an ink, an overprint varnish prepared from a composition (I) of the invention. Compositions (I) of the invention are compatible with most of the radiation curable compounds used in the art. They are further compatible with most additives used standard in the art. An aspect of the invention hence relates to a radiation curable composition (II) that is prepared from a composition (I) according to the invention.
  • An aspect of the invention relates to coating compositions (II) that comprise or are prepared from compositions (I) of the invention.
  • the coating composition (II) is a hard coat composition.
  • a particular embodiment of the invention relates to hardcoats that can be obtained from a composition of the invention.
  • compositions (II) of the invention in particular permit to obtain hardcoats which show after radiation curing a superior chemical resistance against solvents or stains, and a superior mechanical resistance against scratch and abrasion.
  • coatings can be applied to any surface to which the coating of the invention can adhere, either temporarily or permanently.
  • the surfaces may be flexible or rigid.
  • the material can be woven or now-woven.
  • the surface can be made from a material which is fabric, glass, metal, metalloid, metal oxide, ceramic, wood, plastic, resin, rubber, stone, concrete, fittings in electronics, a semiconductor, a particle or a combination thereof.
  • Preferred substrates are metal, wood, and plastics like PVC, PC, ABS, PC/ABS, HIPS, PMMA, and PET.
  • the coatings obtained typically are colorless and transparent and they show superior abrasion resistance, superior scratch resistance, good boiling water resistance and excellent anti-stain or anti-graffiti properties without matting agents for high gloss level or with matting agents for a gloss level at 60° of at most 15, preferably at most 10.
  • the coating surface is smooth and possible to be further formulated to obtain smooth, silky, peach or warm feeling haptic coating.
  • Hardcoats for plastics like PVC, PC, ABS, PC/ABS, HIPS, PMMA, and PET are particularly envisaged in the frame of the invention.
  • the product applications in this industry segment are endless and they can be typically associated to consumer electronics (like mobile phone, computer, television, compact disk) , to automotive plastics for interior applications (like dashboard, trim) or exterior applications (like headlight, mirror, bumper, wheel cover) and to industrial plastics (like film, label, box, toy, sport equipment, garden furniture) , to packaging (vacuum metalization) etc.
  • Hardcoats of the invention can be applied on many materials, substrates and equipments such as appliances, medical devices, cosmetic packaging, consumer electronic goods etc.
  • Hardcoats of the invention after curing typically have Pencil hardness on ABS or PC as measured by appropriate equipment of at least B, preferably at least HB, and most preferably at least F.
  • compositions (II) of the invention are used to make top coats.
  • compositions (I) and (II) of the invention are also suitable for use in overprint varnishes and inks.
  • An aspect of the invention relates to the use of compositions of the invention for the making of coatings (including overprint varnishes) and inks (both for contact and non-contact printing methods like inkjet) .
  • Another aspect concerns the making of these coatings, overprint varnishes and inks from a composition of the invention.
  • the composition of the invention can contain additional pigments and/or colorants.
  • inks, or overprint varnishes comprising a composition of the invention, or prepared from a composition of the invention.
  • Yet another aspect of the invention relates to a process of coating an article or a substrate, at least in part, said method comprising the step of applying a composition of the invention to at least one surface of the article or the substrate, followed by a step of curing using e.g. active energy rays.
  • the active energy rays used for curing preferably are ultraviolet rays, electron beam, X-rays, radioactive rays or high frequency waves. Ultraviolet rays having a wavelength of from 180 to 450 nm are particularly preferred from economical viewpoint. Curing by irradiation may be followed by thermal curing in the presence of suitable external cross linkers.
  • the article or substrate comprises plastic, more in particular is made from plastic such as PVC, PC, ABS, PC/ABS, HIPS, PMMA, or PET.
  • compositions of the invention typically are cured by ultraviolet irradiation, generally in the presence of photo-initiator; they can also be cured by electron-beam irradiation, allowing the use of compositions free of photo-initiator.
  • the compositions according to the invention are providing extremely rapid curing characterized by a higher reactivity allowing higher line speed or less irradiative energy curing and increased productivity.
  • Low energy ultraviolet light sources can also be used (LED lamps) .
  • Coating compositions (II) of the invention typically comprise from 5 to 95%by weight of a radiation curable composition (I) according to the invention.
  • Optionally coating compositions (II) of the invention may comprise from 0 to 30%by weight of at least one organic and/or inorganic matting agent (D) , relative to the total weight of the composition (II) .
  • compositions (II) of the invention are further also suitable for the making of matt coatings.
  • No high loads of matting agents are needed to achieve a satin, matt or even a dead matt effect.
  • a gloss level of at most 80, preferably at most 60, more preferably at most 50 and most preferably at most 45 is obtained at 85° angle.
  • the 60° gloss level is at most 50 (satin) .
  • the 60° gloss level of the matt coating upon curing is at most 5, in particular cases it may even be as low as 1-2.
  • the above gloss levels are for coatings that have a dry thickness (thickness after curing) of 12 ⁇ m. In general the above gloss levels can be obtained for coatings with a dry thickness of from 6 to 120 ⁇ m.
  • matt coating composition (II) of the invention comprise from 5 to 95 % by weight of a radiation curable composition (I) according to the invention and from 0.5 to 30 % by weight of at least one organic and/or inorganic matting agent (D) (like silica and/or waxes) .
  • D organic and/or inorganic matting agent
  • Standard inorganic matting agents include silica (for example amorphous silicon dioxide) , diatomaceous earth, talcum, chalk and waxes.
  • the matting agent is selected from the group consisting of silica, diatomaceous earth, talcum, chalk and mixtures thereof.
  • Silica is often preferred.
  • the silica can be treated or untreated silica, or it can be a mixture of both.
  • inorganic matting agents examples include Acematt TM 3300 (apyrogenic silica) , Acematt TM TS-100, Acematt TM TS-100/20, Acematt TM HK-400, Acematt TM HK-450, Acematt TM 3600, Aerosil TM R-7200 and Aerosil TM R-9200 available from Evonik Degussa; Syloid TM ED5, Syloid TM 162C, Syloid MX TM 306 and Syloid MX TM 309 available from W.R.
  • suitable organic matting agents include organic waxes such as (Methylenediaminomethylether-polycondensate) from Deuteron. Ceraflour TM 988 from BYK is an example of a micronized amide modified polyethylene wax matting agent.
  • suitable examples include LANCO TM 1930 and LANCOWAX TM PP 1362D from Lubrizol, and SASOLWAX TM 5413 from Sasol.
  • compositions (II) hence comprise at least one inorganic matting agent (D1) .
  • Organic solvent (E) can be used to reduce viscosity of compositions (II) of the invention.
  • the organic solvents typically are removed by heating and drying before cure.
  • the heating and drying temperature is preferably, for example, 40°C. or higher to 100°C. or lower.
  • the heating and drying time is, for example, from at least 30 seconds to at most 8 minutes, preferably from at least 1 minute to at most 5 minutes, and more preferably from at least 3 minutes to at most 5 minutes.
  • suitable solvents have been given above (see compounds (C1) ) .
  • solvents, when present, are used in an amount from 0 to 80 %by weight (wt%) , relative to the total weight of the composition (II) . Usually this amount is from 5 to 70 wt%, more preferably from 10 to 60 wt%.
  • compositions (II) of the invention can hence further comprise one or more (meth) acrylated compound (F) .
  • compounds (F) when present, are used in an amount from 0 to 80%by weight (wt%) , relative to the total weight of the composition (II) .
  • this amount is from 0 to 60 wt%, more preferably from 0 to 40 wt%.
  • compound (F) is a reactive diluent.
  • the reactive diluent can be the same as or can be different from (meth) acrylated compounds (C2) listed above.
  • Compounds (F) can also be oligomeric and/or polymeric compounds. Examples thereof are: (poly) urethane (meth) acrylates, (poly) ester (meth) acrylates, (poly) ether (meth) acrylates, epoxy (meth) acrylates and/or (meth) acrylic (meth) acrylates. Such compounds are well known in the art. Preferred are (poly) urethane (meth) acrylates, (poly) ester (meth) acrylates and/or (meth) acrylic (meth) acrylates.
  • Compositions (II) according to the invention typically comprise at least one free-radical thermal initiator and/or at least one photoinitiator.
  • Useful free-radical thermal initiators include, for example, azo, peroxide, persulfate, and redox initiators, and combinations thereof.
  • Useful free-radical photoinitiators include, for example, those known as useful in UV curing of acrylate polymers. Such initiators include aromatic ketones such as benzophenone, anthraquinone, acetophenone, benzoin and benzoin ethers, acylphosphine oxide (APO) and bisaeylphosphine oxide (BAPO) and their derivatives. Free radial photoinitiators are commercially available and include those available from BASF under the trade designation "TRGACURE” , "LUCIRIN” and “DAROCUR” . Combinations of two or more photoinitiators may be used.
  • suitable initiator concentrations are from about 0, 1%to about 10%by weight, particularly suita ble between about 0.5%and about 7%by weight based on the total weight of the reactive compounds a) and b) .
  • the curable composition can be cured at ambient temperature in an inert atmosphere. In a particular embodiment, the curable composition may be cured at ambient temperature in the presence of air.
  • a cure accelerator or synergist can be added in amounts up to 5 %by weight based on the total weight of the curable compounds.
  • cure accelerators include amino functional acrylaf es, such as for example EBECRYL TM PI 16, commercially available from Allnex and Speedcure DMB ⁇ 2-(dimethylamino) benzoate ⁇ available from Lambson.
  • compositions (II) of the invention may further include other optional additives.
  • the compositions may include antistatic agents, wetting agents, dispersants, waxes, leveling agents, light and/or UV-stabilizers, UV-absorbers, ozon stabilizers, antioxidants, inhibitors, fillers, lubricants, pigments, dyes, flow agents and/or viscosifiers.
  • compositions (II) of the invention may be applied in any possible way known in the art and suitable. They may for instance be applied by any coating technique, including the spray, curtain, dip, pad and roll-coating techniques, as well as any printing technique such as lithography, serigraphy, flexography, gravure and inkjet printing.
  • PC stands for polycarbonate.
  • ABS stands for Acrylonitrile butadiene styrene.
  • Solvent resistance acetone double rubs on PC: the solvent resistance is assessed with acetone double rubs (ADR) by pressing a cotton rag saturated with acetone with a backward and forward motion on the coated surface; one double rub is equal to a backward and forward stroke on the coated surface. The reported number is the number of double rubs required to break through the coating. A high solvent resistance (more than hundred acetone double rubs) is necessary to ensure a good protection of the coating and the substrate against any household or industrial product spillage.
  • ADR acetone double rubs
  • RCA test is an abrasion resistance tests performed using a Standard paper as the abrading material. Abrasion is made by pressing the standard paper on the coating with a specific load (175 g usually) . The paper is in contact with a rubber ring on the reverse side. The result is expressed as the number of cycles (corresponds to a certain length of paper) necessary before the substrate starts to show.
  • the conventional (coloured) basecoat has a very poor RCA result (about 5 to 10 cycles) , therefore it does not make a big impact on the result. It is quite easy to see the test limit by the naked eyes, as the plastic substrate is usually of a different colour than the basecoat (prerequisite of the test) .
  • RCA result is also very dependent on the thickness of the clear coating and 2 coatings have to be compared at the same thickness and applied on the same substrate.
  • Pencil hardness The weight load is 750 ⁇ 5 grams. Graded pencils were used and a full assortment consists of several pencils of hardness ranging from 9H (hardest) to 9B (softest) : “H” stands for hardness, “B” stands for blackness and HB is for hard and black pencils. The hardest is 9H, F is the middle of the hardness scale; then comes HB and 9B is the softest.
  • Oil marker pen resistance the oil marker pen is drawn on cured surface of the coating. After the stain was totally dried, it could be removed by dry wipe without aggressive solvents or cleaning agents. The removability was visually judged.
  • Oil marker pen repeating resistance repeat the oil marker pen resistance as above on the same place of the surface until there are traces left visually. The results were expressed by the number of cycles (the drawing and wiping off were recorded as one cycle)
  • Oil marker pen resistance after boiling water the cured surface together with the substrate was placed into boiling water (100 °C) for 1 hour. Then it was taken out for oil marker pen repeating resistance after the water was removed. The results were expressed by the number of cycles (the drawing and wiping off were recorded as one cycle) .
  • the film was visually judged on the presence of defects and scored from 0 to 5. A score 5 corresponds to a coating without defects.
  • UV curing Curing was done in the following way: 6-120 ⁇ m thick coating layers were applied on Leneta paper opacity cards with a bar coater. Coatings were then cured under UV lights at a cure speed of 5 m/min using 40, 80 or 120 Watt/cm 2 Hg lamps.
  • Curing speed Reactivity: a film of 25 ⁇ m is applied on white non absorbing paper and exposed to UV radiations from a 80 W/cm non focalized medium pressure mercury lamp at a defined conveyer speed.
  • the conveyer speed is varied in order to determine the maximum conveyer speed to be used to obtain a fully cured film.
  • the fully cured character of the film is assessed by putting some talc on the surface and rubbing with a finger and then with a cotton. As long as a mat aspect is observed, the film is not fully cured and the conveyer speed must be lowered.
  • the coating is also submitted to 50 double rubs with a wad of cotton drenched in acetone. A fully cured film is not visually affected by this test.
  • the UV-dose expressed in conveyer speed (m/min) with determined lamp power (W/m) necessary to pass the two tests is referred to as the reactivity of the coating
  • Yellowing a film of 25 ⁇ m is applied on white non absorbing paper, cured and exposed to the UV light of an Ultra-Vialux 300W lamp in a completely closed drum. The distance between the lamp and the samples is 50 cm. Yellowing (delta b) is measured with an apparatus type Supercolor immediately after UV exposure and after 48 hours of exposition and compared with the initial yellowing (right after exposure) .
  • Coating compositions were prepared by mixing the components as given in the table below with high speed stirrer. The coating compositions were coated with spray coating application to specific substrates indicated below. The panels were flashed off at 60 °C for 3 min and then UV exposed with 5 m/min for 2 passes with 120 W/cm UV lamp.
  • Amounts are in grams (parts) unless otherwise specified.
  • PETIA penentaerythritol tri/tetra acrylate
  • suitable stabilizers and catalyst into the reactor and heat to 80°C for 7h to obtain a compound (B) , Blended with Compound (A) .

Abstract

L'invention concerne des compositions (I) pouvant durcir par rayonnement qui comportent de 10 à 80 % en poids d'au moins un (méth)acrylate d'uréthane (A) modifié par une silicone, de 0,5 à 60 % en poids d'au moins un composé (méth)acrylé (B) portant au moins 5 groupes (méth)acryloyle par molécule, et, éventuellement, de 10 à 60 % en poids d'au moins un composé (C) différent de (A) ou de (B), les pourcentages en poids étant en rapport avec le poids total de la composition (I). Ces matériaux peuvent être utilisés pour fabriquer des revêtements, des encres et des vernis de surimpression.
PCT/CN2016/101034 2016-09-30 2016-09-30 Compositions pouvant durcir par rayonnement ayant des propriétés anti-taches WO2018058505A1 (fr)

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PCT/CN2016/101034 WO2018058505A1 (fr) 2016-09-30 2016-09-30 Compositions pouvant durcir par rayonnement ayant des propriétés anti-taches
EP17855011.7A EP3519493B1 (fr) 2016-09-30 2017-09-29 Compositions durcissables par rayonnement présentant des propriétés anti-taches
CN201780060526.0A CN109844004B (zh) 2016-09-30 2017-09-29 具有防污性能的辐射可固化组合物
US16/334,424 US11359110B2 (en) 2016-09-30 2017-09-29 Radiation curable compositions with anti-stain properties
PCT/CN2017/104568 WO2018059561A1 (fr) 2016-09-30 2017-09-29 Compositions durcissables par rayonnement présentant des propriétés anti-taches
TW106133549A TWI791464B (zh) 2016-09-30 2017-09-29 具有防污性之輻射可硬化組成物

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EP3620484A1 (fr) * 2018-09-04 2020-03-11 SABIC Global Technologies B.V. Articles de polycarbonate pour appareils électroniques grand public
CN114854304A (zh) * 2022-05-27 2022-08-05 扬州工业职业技术学院 一种具有环保和防污性能的超疏水涂料

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US11359110B2 (en) 2022-06-14
US20190218418A1 (en) 2019-07-18
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TW201817756A (zh) 2018-05-16

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